JP2021155637A - Indicator and adhesive composition for indicator - Google Patents

Abstract

To provide an indicator that can reduce or prevent color irregularities without causing liquid leakage, and allows the replacement timing or the like to be visually confirmed.SOLUTION: An indicator has a chlorine atom-containing resin layer and an adhesive layer containing a dehydrochlorination agent.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to indicators and adhesive compositions.

In recent years, in order to manage the storage period, replacement time, etc., a technique capable of visualizing such various periods has been developed.

Patent Document 1 discloses a temperature-time integration indicator including a temperature-time integration history display composition containing a polyvinylidene chloride-based resin and a basic compound.

Patent Document 2 discloses a life display material for a rubber tube, which is mainly composed of a material that reacts with a material forming the outer surface layer of the rubber tube and changes the color of the outer surface layer over time.

Japanese Unexamined Patent Publication No. 2017-218511 Japanese Unexamined Patent Publication No. 2011-257000

For example, as described in Patent Document 1, in the field of indicators, a dehydrochloric acid agent for changing the color of a polyvinylidene chloride resin is generally used in the form of a solution. When the dehydrochloric acid agent is used in the form of a solution, the solution and a resin having color changing performance such as polyvinylidene chloride resin are separately filled in each section of the packaging material having two sections, for example. An indicator having such a configuration may cause liquid leakage, for example, during transportation or use, or presses a compartment containing a dehydrochloric acid-containing solution of the indicator to obtain such a solution for color change performance. When the solution is allowed to flow into the compartment containing the resin having the above, the solution may not be uniformly applied to the resin, and as a result, color unevenness of the resin having the color changing performance may occur.

Therefore, the subject of the present disclosure is to provide an indicator capable of reducing or preventing color unevenness without causing liquid leakage and visually determining the replacement time or the like.

式１中、
Ｒ¹〜Ｒ^５は、それぞれ独立に、水素又は炭素原子数１〜１０のアルキル基である。但し、Ｒ^１はＲ^３と、Ｒ^２はＲ^５と、それぞれ互いに連結して炭素原子数２〜６のアルキレン基を構成してもよく、また、Ｒ¹〜Ｒ^５の全てが水素の場合を除く。
式２〜式４中、
Ｒは、それぞれ独立に、水素又は炭素原子数１〜２０のアルキル基であり、
式３中、
Ａは、ＨＦ、ＨＣｌ、ＨＢｒ又はＨＩであり、
式４中、
Ｘ⁻は、Ｆ⁻、Ｃｌ⁻、Ｂｒ⁻又はＩ⁻である。
〈態様４〉
前記塩基性化剤が、アルカリ金属水酸化物である、態様３に記載のインジケータ。
〈態様５〉
前記脱塩酸剤が、前記窒素原子含有化合物を含み、かつ、当該窒素原子含有化合物が、１，１，３，３−テトラメチルグアニジン、１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン、尿素、ドデシルアミン塩酸塩、及びラウリルトリメチルアンモニウム＝クロリドから選択される少なくとも一種である、態様３又は４に記載のインジケータ。
〈態様６〉
剥離ライナー、基材、及びバリア層から選択される少なくとも一種をさらに有する、態様１〜５のいずれかに記載のインジケータ。
〈態様７〉
前記塩素原子含有樹脂層と前記接着層とを接触させることによって、色変化反応が開始する、態様１〜６のいずれかに記載のインジケータ。
〈態様８〉
前記塩素原子含有樹脂層と前記接着層とを接触させることが可能な折り返し部を形成し得るように構成された、態様１〜７のいずれかに記載のインジケータ。
〈態様９〉
前記塩素原子含有樹脂層と前記接着層との間に、引き抜き可能な剥離ライナーを備える、態様１〜７のいずれかに記載のインジケータ。
〈態様１０〉
前記接着層の上に、剥離ライナー及び前記塩素原子含有樹脂層を交互に重ねた構成を有し、前記塩素原子含有樹脂層を前記剥離ライナーから剥がした後に、前記剥離ライナーを前記接着層から剥がし、その後に、前記塩素原子含有樹脂層を前記接着層に接触させ得るように構成された、態様１〜７のいずれかに記載のインジケータ。
〈態様１１〉
−５０℃以上の環境下で使用される、態様１〜１０のいずれかに記載のインジケータ。
〈態様１２〉
脱塩酸剤を含む、態様１〜１１のいずれかに記載のインジケータ用の接着剤組成物。 <Aspect 1>
An indicator having a chlorine atom-containing resin layer and an adhesive layer containing a dehydrochloric acid agent.
<Aspect 2>
The indicator according to aspect 1, wherein the chlorine atom-containing resin layer contains at least one selected from a polyvinyl chloride-based resin and a polyvinylidene chloride-based resin.
<Aspect 3>
The dehydrochloric acid agent is selected from an amine, a nitrogen atom-containing compound represented by the following formula 1, and a mixture of at least one nitrogen atom-containing compound selected from the following formulas 2 to 4 and a basicizing agent. The indicator according to aspect 1 or 2, which is at least one of the following:

In formula 1,
R ^{1 to} R ⁵ are independently hydrogen or alkyl groups having 1 to 10 carbon atoms. However, R ¹ may ^{be linked to R 3} and R ² to R ⁵ to form an alkylene group having 2 to 6 carbon atoms, and when all of ^{R 1 to} R ^{5 are hydrogen.} except for.
In formulas 2 to 4,
R is independently an alkyl group having 1 to 20 carbon atoms or hydrogen.
In formula 3,
A is HF, HCl, HBr or HI,
In formula 4,
X ⁻ is F ⁻ , Cl ⁻ , Br ⁻ or I ⁻ .
<Aspect 4>
The indicator according to aspect 3, wherein the basicizing agent is an alkali metal hydroxide.
<Aspect 5>
The dehydrochloride agent contains the nitrogen atom-containing compound, and the nitrogen atom-containing compound is 1,1,3,3-tetramethylguanidine, 1,5,7-triazabicyclo [4.4.0. The indicator according to aspect 3 or 4, wherein it is at least one selected from deca-5-ene, urea, dodecylamine hydrochloride, and lauryltrimethylammonium-chloride.
<Aspect 6>
The indicator according to any of aspects 1-5, further comprising at least one selected from a release liner, a substrate, and a barrier layer.
<Aspect 7>
The indicator according to any one of aspects 1 to 6, wherein the color change reaction is started by bringing the chlorine atom-containing resin layer into contact with the adhesive layer.
<Aspect 8>
The indicator according to any one of aspects 1 to 7, which is configured to form a folded portion capable of bringing the chlorine atom-containing resin layer into contact with the adhesive layer.
<Aspect 9>
The indicator according to any one of aspects 1 to 7, wherein a pullable release liner is provided between the chlorine atom-containing resin layer and the adhesive layer.
<Aspect 10>
It has a structure in which a release liner and a chlorine atom-containing resin layer are alternately laminated on the adhesive layer, and after the chlorine atom-containing resin layer is peeled off from the release liner, the release liner is peeled off from the adhesive layer. The indicator according to any one of aspects 1 to 7, which is configured so that the chlorine atom-containing resin layer can be brought into contact with the adhesive layer.
<Aspect 11>
The indicator according to any of aspects 1-10, used in an environment of −50 ° C. or higher.
<Aspect 12>
The adhesive composition for an indicator according to any one of aspects 1-11, comprising a dehydrochloric acid agent.

According to the present disclosure, it is possible to provide an indicator capable of reducing or preventing color unevenness without causing liquid leakage and visually determining a replacement time or the like.

(A) is a schematic cross-sectional view of an indicator before the start of use, comprising a laminate in which the indicator adhesive composition of one embodiment of the present disclosure is applied to a base material and a chlorine atom-containing resin layer, and (b). Is a schematic cross-sectional view of a state in which the adhesive layer containing the dehydrochloric acid agent of the laminate and the chlorine atom-containing resin layer are brought into contact with each other to start the color change of the indicator. (A) is a schematic cross-sectional view of an indicator before the start of use of another embodiment of the present disclosure, and (b) is an indicator in which an adhesive layer containing a dehydrochloric acid agent and a chlorine atom-containing resin layer are brought into contact with each other. It is the schematic cross-sectional view of the state which started the color change. (A) is a schematic cross-sectional view of an indicator before the start of use of another embodiment of the present disclosure, and (b) is an indicator in which an adhesive layer containing a dehydrochloric acid agent and a chlorine atom-containing resin layer are brought into contact with each other. It is the schematic cross-sectional view of the state which started the color change. (A) is a schematic cross-sectional view of an indicator before the start of use of another embodiment of the present disclosure, and (b) is interposed between an adhesive layer containing a dehydrochloric acid agent and a chlorine atom-containing resin layer. It is a schematic cross-sectional view of a state in which a release liner is removed, and (c) is a schematic cross-sectional view of a state in which an adhesive layer containing a dehydrochloric acid agent and a chlorine atom-containing resin layer are brought into contact with each other to start color change of an indicator. be. The state of the color change of the indicator of one embodiment of the present disclosure which has an adhesive layer containing 1,1,3,3-tetramethylguanidine as a dehydrochloric acid agent and polyvinylidene chloride film as a chlorine atom-containing resin layer is shown. It is a photograph.

Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist of the invention.

The indicators of the present disclosure have a chlorine atom-containing resin layer and an adhesive layer containing a dehydrochloric acid agent.

Although not limited by the principle, such an indicator can reduce or prevent color unevenness without causing liquid leakage, and can visually determine the replacement time and the like. The principle is considered as follows.

Regarding liquid leakage, since the adhesive layer containing the dehydrochloric acid agent is applied to the indicator in a solid form rather than a solution form, it is considered that a situation in which liquid leakage does not occur cannot occur.

Regarding color unevenness, for example, as described in Patent Document 1, an indicator having a configuration in which a chlorine atom-containing resin and a solution containing a dehydrochloric acid agent are separately filled in each section of a packaging material having two sections. In the case of, the application of the solution to the chlorine atom-containing resin as a result of the inflow amount of the solution into the compartment containing the chlorine atom-containing resin differs depending on the degree of pressing applied to the compartment containing the dehydrochloric acid agent-containing solution of the indicator. Since the states are different, it is considered that color unevenness is likely to occur.

On the other hand, in the indicator of the present disclosure, since the surface of the adhesive layer containing the dehydrochloric acid agent substantially uniformly and the surface of the chlorine atom-containing resin layer may be simply bonded, the dehydrochloric acid agent is applied to the chlorine atom-containing resin. It is considered that color unevenness can be reduced or prevented as compared with the case of applying a solution containing chlorine, and as a result, it is possible to visually and better determine when to replace a product or the like with an indicator.

In addition to amines generally used in the field of indicators, the present inventor uses a specific nitrogen atom-containing compound or a mixture of a specific nitrogen atom-containing compound and a basicizing agent in the same manner as amines. , Found that the color of a chlorine atom-containing resin can be changed.

For example, 1,1,3,3-tetramethylguanidine included in the compound of formula 1 can change the color of a chlorine atom-containing resin by itself or in combination with a basicizing agent, but guanidine, Alternatively, arginine having a guanidine structure could not change the color of the chlorine atom-containing resin at a visible level when used alone or in combination with a basicizing agent. Further, the urea contained in the compound of the formula 2 can change the color of the chlorine atom-containing resin when used in combination with the basicizing agent, but the color of the chlorine atom-containing resin cannot be changed by urea alone. ..

From this, the color changing action of the chlorine atom-containing resin is not an action that can be exerted by any nitrogen atom-containing compound, and is not an action that can be exerted by any nitrogen atom-containing compound when used in combination with a basicizing agent. A nitrogen atom-containing compound having a specific structure as represented by the above formula 1, or a nitrogen atom-containing compound having a specific structure as represented by the above formulas 2 to 4, and a basicizing agent. It is considered that this is an effect that can be achieved when the above is used in combination.

"indicator"
The indicator of the present disclosure is a performance in which the degree of coloring of the chlorine atom-containing resin layer changes according to the temperature and / or time when the chlorine atom-containing resin layer and the adhesive layer containing a dehydrochloric acid agent are brought into contact with each other (“color change performance”). It may be called.). As a result, by confirming the degree of coloring of the chlorine atom-containing resin layer in the indicator, it is possible to confirm the optimum replacement time of the product or the like with the indicator.

The color change performance of the indicator of the present disclosure can be evaluated by, for example, the uniformity of color change by the color change test described later, and in such a test, "A" intended to exhibit uniform color change performance. You can get an evaluation.

The color change performance of the indicator of the present disclosure can be evaluated by, for example, the end point L value by the color change test described later. The end point L value of the indicator of the present disclosure includes, for example, 80.0 or less, 75.0 or less, 70.0 or less, 65.0 or less at a storage temperature of 0 ° C., 23 ° C., or 40 ° C. It can be 60.0 or less, 55.0 or less, 50.0 or less, 45.0 or less, 40.0 or less, 35.0 or less, or 30.0 or less, and 5.0 or more and 10. It can be 0 or more, 15.0 or more, 20.0 or more, 25.0 or more, or 30.0 or more.

The color change performance of the indicator of the present disclosure can be evaluated by, for example, the ΔL value obtained by the color change test described later. The ΔL value of the indicator of the present disclosure includes, for example, 10.0 or more, 15.0 or more, 20.0 or more, 25.0 or more, 30 at a storage temperature of 0 ° C., 23 ° C., or 40 ° C. It can be 0.0 or more, 35.0 or more, 40.0 or more, 45.0 or more, 50.0 or more, or 55.0 or more, and 70.0 or less, 65.0 or less, 60.0. Below, it can be 55.0 or less, 50.0 or less, 45.0 or less, 40.0 or less, 35.0 or less, or 30.0 or less.

The color change performance of the indicator of the present disclosure can be evaluated by, for example, the time until the indicator changes to an L value in the range of 30 ± 3 or 70 ± 3 by the color change speed test described later. The time until the indicator of the present disclosure changes to a predetermined L value can be appropriately adjusted depending on the concentration of the dehydrochloric acid agent and the like. Such time is, for example, 10 years or less, 5 years or less, 1 year or less, 6 months or less, 3 months or less, 1 at any storage temperature of 0 ° C., 23 ° C., or 40 ° C. Month or less, 20 days or less, 10 days or less, 5 days or less, 3 days or less, 60 hours or less, 50 hours or less, 40 hours or less, 30 hours or less, 25 hours or less, 20 hours or less, 15 hours or less, 10 hours or less , 7 hours or less, or 5 hours or less, and 10 minutes or more, 20 minutes or more, 30 minutes or more, 1 hour or more, 5 hours or more, 10 hours or more, 15 hours or more, 1 day or more, 3 It can be days or more, 5 days or more, 10 days or more, 20 days or more, 1 month or more, 3 months or more, 6 months or more, or 1 year or more.

In some embodiments, the odor of the adhesive composition that can be used in the indicators of the present disclosure can be evaluated, for example, in an odor test described below, which is intended to be odorless. You can get an evaluation of "nothing".

<Chlorine atom-containing resin layer>
The indicators of the present disclosure have a chlorine atom-containing resin layer. The chlorine atom-containing resin layer may be in the form of, for example, a coating layer, a film, a sheet, or the like. For example, when a chlorine atom-containing resin layer is applied to a base material, the resin layer is applied to the entire surface of the base material. It may be applied partially to the substrate.

The chlorine atom-containing resin layer may be transparent, translucent, or opaque in the visible region in whole or in part. Here, in the present disclosure, "transparent" is intended to be an optical property capable of visually recognizing a color change. The degree of transparency can be evaluated by, for example, the average transmittance in the visible light region (wavelength 400 nm to 700 nm) measured in accordance with JIS K 7375. Specifically, the average transmittance is 80% or more. It is preferably 85% or more, or 90% or more. The upper limit of the average transmittance is not particularly limited, but may be, for example, less than 100%, 99% or less, or 98% or less. Further, in the present disclosure, "semi-transparent" means that the average transmittance in the visible light region (wavelength 400 nm to 700 nm) measured in accordance with JIS K 7375 is less than 80%, preferably 75% or less. It is intended that the substrate is not completely concealed, and "opaque" in the present disclosure is intended to completely conceal the substrate.

The chlorine atom-containing resin that can be used for the chlorine atom-containing resin layer is not particularly limited, and for example, at least one selected from polyvinyl chloride-based resin and polyvinylidene chloride-based resin can be used.

The blending ratio of the chlorine atom-containing resin in the chlorine atom-containing resin layer is not particularly limited, but is, for example, 50% by mass or more, 70% by mass or more, 80% by mass or more, based on the total amount of the chlorine atom-containing resin layer. Alternatively, it can be 90% by mass or more. The upper limit of the blending ratio is not particularly limited, but may be, for example, 100% by mass or less or less than 100% by mass.

(Polyvinyl chloride resin)
The polyvinyl chloride-based resin (sometimes referred to as "PVC") is not particularly limited, but may be, for example, a vinyl chloride homopolymer (polyvinyl chloride resin) and has other properties (for example, a machine). For the purpose of imparting properties), it may be a copolymer of vinyl chloride and other monomers copolymerizable therewith. The copolymer may be a graft copolymer, a block copolymer or a random copolymer. These resins can be used alone or in combination of two or more.

Examples of other monomers constituting the copolymer include olefins such as ethylene, propylene and butene; vinyl esters of saturated acids such as vinyl acetate and vinyl laurate; unsaturated acids such as acrylic acid methyl ester and methacrylate methyl ester. Alkyl esters of acids; alkyl vinyl ethers such as lauryl vinyl ethers; maleic acid, acrylonitrile, styrene, methylstyrene, vinylidene fluoride; and the like. These monomers can be used alone or in combination of two or more.

When the polyvinyl chloride resin is a copolymer, the content of other monomer units in the copolymer shall be 1% by mass or more, 5% by mass or more, or 10% by mass or more based on the total amount of monomer units. Can be done. The upper limit of the content of other monomer units in the copolymer is not particularly limited, and is, for example, 90% by mass or less, 70% by mass or less, 50% by mass or less, or 40% by mass or less based on the total amount of monomer units. Can be done.

The content of the vinyl chloride unit in the copolymer can be 10% by mass or more, 30% by mass or more, 50% by mass or more, or 60% by mass or more based on the total amount of the monomer units. The upper limit of the content of the vinyl chloride unit in the copolymer is not particularly limited, and can be, for example, 99% by mass or less, 95% by mass or less, or 90% by mass or less based on the total amount of the monomer units.

(Polyvinylidene chloride resin)
The polyvinylidene chloride-based resin (sometimes referred to as “PVDC”) is not particularly limited, but may be, for example, a vinylidene chloride homopolymer (polyvinylidene chloride resin) and has other properties (for example, a machine). For the purpose of imparting properties), it may be a copolymer of vinylidene chloride and another monomer copolymerizable therewith. The copolymer may be a graft copolymer, a block copolymer or a random copolymer. These resins can be used alone or in combination of two or more.

Other monomers copolymerizable with vinylidene chloride include, for example, vinyl chloride; acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and lauryl acrylate (alkyl groups having 1 to 18 carbon atoms). Alkyl methacrylate esters such as methyl methacrylate, butyl methacrylate and lauryl methacrylate (1 to 18 carbon atoms in the alkyl group); vinyl cyanide such as acrylonitrile; aromatic vinyl such as styrene; carbon atoms such as vinyl acetate Vinyl esters of aliphatic carboxylic acids of number 1-18; Alkyl vinyl ethers of carbon atoms 1-18; Vinyl polymerizable unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid; maleic acid, fumaric acid, Examples thereof include alkyl esters of vinyl polymerizable unsaturated carboxylic acids such as itaconic acid (including partial esters and having 1 to 18 carbon atoms in the alkyl group). Among them, at least one selected from the group consisting of vinyl chloride, methyl acrylate and lauryl acrylate is preferable. These monomers can be used alone or in combination of two or more.

When the polyvinylidene chloride resin is a copolymer, the content of other monomer units in the copolymer is 2% by mass or more, 3% by mass or more, 4% by mass or more, or 5% by mass based on the total amount of monomer units. It can be% or more. The upper limit of the content of other monomer units in the copolymer is not particularly limited, and is, for example, 40% by mass or less, 35% by mass or less, 25% by mass or less, or 22% by mass or less based on the total amount of monomer units. Can be done.

The content of vinylidene chloride unit in the copolymer can be 60% by mass or more, 65% by mass or more, 75% by mass or more, or 78% by mass or more based on the total amount of monomer units. The upper limit of the content of vinylidene chloride unit in the copolymer is not particularly limited, and may be, for example, 98% by mass or less, 97% by mass or less, 96% by mass or less, or 95% by mass or less based on the total amount of monomer units. can.

(Arbitrary ingredient)
The chlorine atom-containing resin layer may contain arbitrary components such as additives and resins other than the chlorine atom-containing resin as long as the effects of the present invention are not affected.

Examples of the additive include various additives such as a heat stabilizer, a plasticizer, a processing aid, a colorant (for example, a pigment, a dye), an ultraviolet absorber, a pH adjuster, and a dispersion aid. These can be used alone or in combination of two or more. For example, from the viewpoint of improving the visibility of color change, it is preferable to use a colorant that exhibits white color as an additive.

Other resins other than the chlorine atom-containing resin include, for example, polyethylene wax, polyethylene oxide wax, polyethylene (low density polyethylene or high density polyethylene), ethylene-vinyl acetate copolymer, homopolymer or co-weight of acrylic acid ester. Examples thereof include coalescence, homopolymers or copolymers of methacrylic acid esters, and methyl methacrylate-butadiene-styrene copolymers. These can be used alone or in combination of two or more.

(Thickness of chlorine atom-containing resin layer)
The thickness of the chlorine atom-containing resin layer is not particularly limited and can be appropriately selected according to the required color change performance and the like. The thickness of the chlorine atom-containing resin layer can be, for example, 1 μm or more, 5 μm or more, 10 μm or more, 30 μm or more, or 50 μm or more, and 1 mm or less, 500 μm or less, 200 μm or less, or 100 μm or less. Can be done. In the present disclosure, when the thickness of each layer of the indicator is thick and can be measured independently, a high-precision digital micrometer (MDH-25MB, manufactured by Mitutoyo Co., Ltd.) is used. The thickness of any portion of the layer to be measured can be defined as an average value calculated by measuring at least 5 times. Alternatively, for example, when the thickness of the layers is thin and it is difficult to measure, the thickness of each layer constituting the indicator is determined by measuring the cross section in the thickness direction of the laminated structure using a scanning electron microscope. It can be defined as the average value of the thickness of any at least 5 points in the target layer, for example, the chlorine atom-containing resin layer.

<Adhesive layer containing dehydrochloric acid>
The indicators of the present disclosure have an adhesive layer containing a dehydrochloric acid agent. The adhesive layer may be in the form of, for example, a coating layer, and for example, when the adhesive layer is applied to the base material, the adhesive layer may be applied to the entire surface of the base material, or to the base material. May be partially applied. The adhesive layer may be transparent, translucent, or opaque in the visible region in whole or in part.

(Dehydrochloric acid agent)
The dehydrochloric acid agent is not particularly limited as long as it can dehydrochlorate a chlorine atom-containing resin to change its color. For example, amine, a nitrogen atom-containing compound represented by the following formula 1, and the following formula 2 ~ At least one selected from a mixture of at least one nitrogen atom-containing compound selected from the formula 4 and a basicizing agent can be used.

As described in Patent Document 1, amine is an agent generally used as a dehydrochloric acid agent for indicators, but has a specific odor (this odor is referred to as "amine odor"). It may be called.). On the other hand, the present inventor has found that the nitrogen atom-containing compound represented by the following formula 1 and the mixture of at least one nitrogen atom-containing compound selected from the following formulas 2 to 4 and the basicizing agent have an amine odor. It has been found that the chlorine atom-containing resin can exhibit a dehydrochloric acid action, that is, a color changing action, similarly to amines, even though it does not exhibit such an offensive odor. Therefore, from the viewpoint of reducing offensive odors such as amine odors, among the above-mentioned dehydrochloric acid agents, nitrogen atom-containing compounds represented by the following formula 1 and at least one selected from the following formulas 2 to 4 It is preferable to use at least one selected from a mixture of a nitrogen atom-containing compound and a basicizing agent.

a. Amines The amines that can be used as dehydrochlorination agents are not particularly limited, and examples thereof include alicyclic amines, acyclic aliphatic amines, aromatic amines, and the like. From the viewpoint of safety and the like, alicyclic amines are used. Is preferable. The number of carbon atoms in such an amine is not particularly limited, and is, for example, 1 to 10, preferably 2 to 8, and more preferably 3 to 6. The total number of amino groups (that is, -NH ₂ ) and substituted amino groups (groups obtained by substituting the hydrogen atom of the amino group with an organic group such as an alkyl group (for example, methyl group or ethyl group)) in the amine. Is not particularly limited, and is, for example, 1 to 3, preferably 1 or 2, and more preferably 1. The amine may have a substituent. The substituent is not particularly limited, and examples thereof include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group, and a nitro group. The amine may have a heteroatom in the carbon chain. These amines can be used alone or in combination of two or more.

The alicyclic amine is not particularly limited, and examples thereof include pyrrolidine, piperidine, 1-methylpiperidine, 2-methylpiperidine, hexamethyleneimine, and morpholine, and piperidine is preferable from the viewpoint of reactivity and the like. The acyclic aliphatic amine is not particularly limited, and examples thereof include trimethylamine, triethylamine, tripropylamine, and trypentylamine, and trimethylamine is preferable from the viewpoint of reactivity and the like. The aromatic amine is not particularly limited, and examples thereof include aniline and the like. In particular, as the amine, piperidine is preferable from the viewpoint of reactivity of dehydrochloric acid and the like.

The amine can function as a dehydrochloric acid agent by itself, but may be used in combination with a basicizing agent described later.

b. Nitrogen atom-containing compound represented by the formula 1 Examples of the nitrogen atom-containing compound that can be used as the dehydrochloric acid agent include the nitrogen atom-containing compound represented by the following formula 1.

In Formula 1, R ^{1 to} R ⁵ are independently hydrogen or alkyl groups having 1 to 10 carbon atoms. However, R ¹ may ^{be linked to R 3} and R ² to R ⁵ to form an alkylene group having 2 to 6 carbon atoms, and when all of ^{R 1 to} R ^{5 are hydrogen.} except for.

In formula 1, when R ¹ and R ³ and R ² and R ^{5 are not connected, R 5 in} formula 1 may be hydrogen from the viewpoint of color changeability, low odor, and the like. Preferably, the ^{number of carbon atoms of the alkyl group in R 1 to} R ⁴ is preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3. Among them, as such a nitrogen atom-containing compound, ^{1,1,3,3-tetramethylguanidine in which all of R 1 to} R ⁴ are methyl groups and R ⁵ is hydrogen is most preferable.

In formula 1, when R ¹ and R ³ and R ² and R ^{5 are connected, R 4 in} formula 1 may be hydrogen from the viewpoint of color changeability, low odor, and the like. Preferably, ^{the connecting portions of R 1} and R ³ and R ² and R ⁵ each form an alkylene group having 2 to 4 carbon atoms, and each form an alkylene group having 2 to 3 carbon atoms. Is more preferable. Among them, as such a nitrogen atom-containing compound, 1,5,7-triazabicyclo [in which the connecting portion of ^{R 1} and R ³ and R ² and R ^{5 is a propylene group and R 4 is hydrogen.} 4.4.0] Deca-5-ene is most preferable.

Since the boiling point or decomposition temperature of the nitrogen atom-containing compound of the formula 1 is higher than, for example, the boiling point of piperidine (106 ° C.) described above and it is difficult to volatilize, the indicator is manufactured, for example, in the process of drying the adhesive layer. Changes in the concentration of such compounds can be reduced or suppressed as compared with the case of using piperidine.

The action of reducing or suppressing the change in the concentration of the nitrogen atom-containing compound in the drying step is not limited to the nitrogen atom-containing compound of Formula 1, and has a boiling point higher than the boiling point of piperidine by 10 ° C. or higher, 20 ° C. or higher, or 30 ° C. or higher. Alternatively, a nitrogen atom-containing compound having a decomposition temperature can be used in the same manner. The temperature of the drying step when forming the adhesive layer using the adhesive composition containing such a nitrogen atom-containing compound is 50 ° C. or higher, 60 ° C. or higher, 70 ° C. or higher, or 80 ° C. or higher. It can also be 120 ° C. or lower, 110 ° C. or lower, or 100 ° C. or lower.

The nitrogen atom-containing compound of the formula 1 can function as a dehydrochloric acid agent by itself, but may be used in combination with a basicizing agent described later.

c. Mixture of at least one nitrogen atom-containing compound selected from formulas 2 to 4 and a basicizing agent As a dehydrochloric acid agent, at least one nitrogen atom-containing compound selected from formulas 2 to 4 and a basicizing agent Mixtures can be used.

c-1. At least one nitrogen atom-containing compound selected from formulas 2 to 4 As a nitrogen atom-containing compound that can function as a dehydrochloric acid agent in combination with a basicizing agent, a nitrogen atom-containing compound represented by the following formula 2 is used. Can be mentioned:

R in the nitrogen atom-containing compound of the formula 2 is independently hydrogen or an alkyl group having 1 to 20 carbon atoms, but from the viewpoint of color change performance, low odor, etc., the number of carbon atoms of the alkyl group in R is Of the above, 1 to 10 is preferable, 1 to 8 is more preferable, 1 to 5 is further preferable, and 1 to 3 is particularly preferable. Among them, as the nitrogen atom-containing compound of the formula 2, urea in which all of R is hydrogen is most preferable.

Examples of the nitrogen atom-containing compound that can function as a dehydrochloric acid agent in combination with a basicizing agent include a nitrogen atom-containing compound represented by the following formula 3.

R in the nitrogen atom-containing compound of the formula 3 (sometimes referred to as "amine salt") is hydrogen or an alkyl group having 1 to 20 carbon atoms, respectively, and A is HF, HCl, HBr or HI. From the viewpoint of color change performance, low odor, etc., the number of carbon atoms of the alkyl group in R is preferably 15 or less, 14 or less, 13 or less, or 12 or less, and 1 or more, 2 or more, 3 or more, 4 or more, Or 5 or more is preferable, and 2 out of 3 Rs are more preferably hydrogen. Regarding A in the formula 3, HCl or HBr is preferable, and HCl is more preferable. Among them, dodecylamine hydrochloride is most preferable as the nitrogen atom-containing compound of the formula 3.

Examples of the nitrogen atom-containing compound that can function as a dehydrochloric acid agent in combination with a basicizing agent include a nitrogen atom-containing compound represented by the following formula 4.

In the nitrogen atom-containing compound of the formula 4 (sometimes referred to as "quaternary ammonium salt"), R is independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and X ⁻ is. F ⁻ , Cl ⁻ , Br ⁻ or I ⁻ . From the viewpoint of color change performance, low odor, etc., the number of carbon atoms of the alkyl group in R is preferably 15 or less, 14 or less, 13 or less, or 12 or less, and 1 or more, 2 or more, 3 or more, 4 or more, Alternatively, 5 or more is preferable, three of the four Rs are the same, and the number of carbon atoms of the alkyl group of these three Rs is preferably 1 to 8, more preferably 1 to 5, and 1 ~ 3 is particularly preferable, and the number of carbon atoms of the remaining R alkyl group is preferably 10 to 15, more preferably 10 to 13, and particularly preferably 10 to 12. ^{Regarding X −} in the formula 4, Cl ⁻ or Br ⁻ is preferable, and Cl ⁻ is more preferable. Of these, lauryltrimethylammonium = chloride is the most preferable as the nitrogen atom-containing compound of the formula 4.

c-2. Basic agent The basic agent is not particularly limited as long as it is an agent capable of making the pH of the adhesive composition capable of forming an adhesive layer more basic, and for example, an alkali metal hydroxide may be used. can. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, and among them, sodium hydroxide is preferable from the viewpoint of color change performance and the like.

d. Content of amine, nitrogen atom-containing compound of formulas 1 to 4 and basicizing agent The content of amine and nitrogen atom-containing compound of formulas 1 to 4 is not particularly limited and depends on the required color change performance and the like. It can be selected as appropriate. For example, the content is 0.1% by mass or more, 0.5% by mass or more, 1.0% by mass or more, 3.0% by mass or more, 5.0% by mass or more, based on the total amount of the adhesive layer. It can be 7.0% by mass or more, 10% by mass or more, or 15% by mass or more. The upper limit of this content is not particularly limited, but may be, for example, 50% by mass or less, 40% by mass or less, 30% by mass or less, or 20% by mass or less from the viewpoint of adhesiveness and the like.

The content of the basicizing agent is not particularly limited and can be appropriately selected depending on the required color change performance and the like. For example, the content is 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, based on the total amount of the adhesive layer. It can be 1.0% by mass or more, 2.0% by mass or more, or 3.0% by mass or more. The upper limit of this content is not particularly limited, but from the viewpoint of adhesiveness and the like, for example, 10% by mass or less, 5.0% by mass or less, 3.0% by mass or less, or 1.0% by mass or less. can do.

(glue)
The adhesive used in the adhesive layer is not particularly limited, and a known adhesive can be used. For example, use solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, thermosetting or UV-curable adhesives such as acrylic, methacrylic, polyolefin, polyurethane, polyester, polyether, and rubber. can do.

(Arbitrary ingredient)
Arbitrary components such as various additives can be blended in the adhesive layer as long as the effects of the present invention are not affected.

Examples of the additive include various additives such as a heat stabilizer, a plasticizer, a processing aid, a colorant (for example, a pigment and a dye), an ultraviolet absorber, a pH adjuster, and a dispersion aid. These can be used alone or in combination of two or more. For example, from the viewpoint of improving the visibility of color change, it is preferable to use a colorant that exhibits white color as an additive.

(Thickness of adhesive layer)
The thickness of the adhesive layer is not particularly limited, and can be appropriately selected according to the required color change performance, adhesiveness, and the like. The thickness of the adhesive layer can be, for example, 1 μm or more, 5 μm or more, 10 μm or more, or 20 μm or more, and can be 50 μm or less, 40 μm or less, or 30 μm or less.

(Adhesive composition)
The adhesive layer containing the dehydrochloric acid agent in the indicators of the present disclosure can be prepared by using an adhesive composition containing various components described above that can constitute the adhesive layer.

The adhesive composition is, for example, a mixture of an organic solvent (for example, a water-insoluble organic solvent such as methyl ethyl ketone) and an aqueous solvent (for example, water, water and a water-soluble organic solvent such as ethanol) in consideration of coating property and the like. Solvent, etc.), leveling agent, etc. can be included.

In some embodiments, the adhesive compositions for indicators of the present disclosure can exhibit basicity. The pH of such a composition is not particularly limited, but from the viewpoint of color change performance and the like, the pH of the composition can be, for example, 10.0 or more, 11.0 or more, or 12.0 or more. Further, it can be 14.0 or less, 13.5 or less, or 13.0 or less. Here, the pH of the composition is, for example, a glass electrode measurement method at 25 ° C. using a pH meter (desktop pH / water quality analyzer F74, electrode: long ToupH electrode 9680S-10D) manufactured by HORIBA, Ltd. Can be measured by.

The means for preparing the adhesive layer using the adhesive composition for the indicator of the present disclosure is not particularly limited, and for example, known printing methods such as gravure direct printing, gravure offset printing, inkjet printing, laser printing, and screen printing. Alternatively, known coating methods such as gravure coating, roll coating, die coating, bar coating, and knife coating can be adopted.

<Any layer>
In some embodiments, the indicators of the present disclosure may further include additional layers, such as, for example, a release liner, a substrate, a barrier layer, etc., as optional components. These layers can be adopted alone or in combination of two or more.

(Peeling liner)
When applied to an adhesive layer, a chlorine atom-containing resin layer, or the like, the release liner can be used as a component that can be temporarily attached and, if necessary, can be peeled off from those layers. Can be done.

The material of the release liner is not particularly limited, and for example, paper (for example, kraft paper), polymer material (for example, polyolefin such as polyethylene or polypropylene, ethylene vinyl acetate, polyurethane, polyester such as polyethylene terephthalate) and the like may be used. Can be done. If necessary, a layer prepared by a release agent such as a silicone-containing material or a fluorocarbon-containing material may be applied to the surface of the release liner.

The release liner can be in the form of, for example, a film, a sheet, a plate or the like. The thickness of the release liner is not particularly limited, and can be, for example, 5 μm or more, 10 μm or more, or 20 μm or more, and can be 1 mm or less, 500 μm or less, 300 μm or less, 200 μm or less, or 150 μm or less.

(Base material)
The base material can be used as a support for, for example, a chlorine atom-containing resin layer, an adhesive layer, or any other layer. The substrate may be transparent, translucent, or opaque in the visible region in whole or in part. Further, the surface of the base material may be subjected to surface treatment such as corona treatment or plasma treatment.

The material of the base material is not particularly limited, and resins other than chlorine atom-containing resin, for example, polyurethane resin, polyolefin resin such as polyethylene, polyester resin such as polyethylene terephthalate (PET), polycarbonate resin, polyimide resin, polyamide such as nylon, etc. Resins, acrylic resins, methacrylic resins, fluororesins and the like can be used. These can be used alone or in combination of two or more.

The base material can be in the form of, for example, a film, a sheet, a plate-like material, or the like. The thickness of the base material is not particularly limited, and may be, for example, 50 μm or more, 80 μm or more, or 100 μm or more, and may be 1 mm or less, 500 μm or less, 300 μm or less, 200 μm or less, or 150 μm or less.

(Barrier layer)
The barrier layer can be used, for example, as a layer for suppressing the invasion of water and the like, the volatilization of the dehydrochloric acid agent, and the contact between the adhesive layer containing the dehydrochloric acid agent and the chlorine atom-containing resin layer.

The barrier layer is not particularly limited, and for example, polyurethane resin, polyolefin resin such as polyethylene, polyester resin such as polyethylene terephthalate (PET), polycarbonate resin, polyimide resin, polyamide resin, acrylic resin, methacrylic resin, fluororesin, ethylene- Examples thereof include layers prepared from resin materials such as vinyl alcohol copolymers (EVOH), polyacrylonitrile (PAN), and ethylene-based unsaturated polymers such as cyclic olefin-based polymers, and aluminum vapor-deposited films and silica-deposited films. , Silicon nitride vapor-deposited film, alumina vapor-deposited film, or inorganic material vapor-deposited film such as silica-alumina dual vapor-deposited film. These can be used alone or in combination of two or more.

The thickness of the barrier layer is not particularly limited, and can be, for example, 50 nm or more, 100 nm or more, 500 nm or more, 1 μm or more, 5 μm or more, 10 μm or more, 30 μm or more, or 50 μm or more, and 100 μm or less, 70 μm or less. It can be 50 μm or less, or 30 μm or less.

(Arbitrary ingredient)
Any component such as various additives can be blended in any layer such as a release liner, a base material, and a barrier layer as long as the effect of the present invention is not affected.

Examples of the additive include various additives such as a heat stabilizer, a plasticizer, a processing aid, a colorant (for example, a pigment and a dye), an ultraviolet absorber, a pH adjuster, and a dispersion aid. These can be used alone or in combination of two or more. For example, when a colorant exhibiting white color is added to the base material and the barrier layer, the visibility of the color change can be improved.

<Indicator configuration>
The indicator of the present disclosure starts a color change reaction when the chlorine atom-containing resin layer and the adhesive layer containing a dehydrochloric acid agent come into contact with each other. Therefore, prior to using the indicator, it is typically desirable that the indicator be configured so that the chlorine atom-containing resin layer and the adhesive layer containing the dehydrochloric acid agent do not come into contact with each other. Hereinafter, the configuration of the indicator will be described with reference to the drawings, but the configuration of the indicator is not limited thereto.

FIG. 1 shows an indicator 100 composed of a laminate including a base material 101 and an adhesive layer 103 containing a dehydrochloric acid agent, and a chlorine atom-containing resin layer 105. Such an indicator may be provided, for example, in a configuration such as a kit in which the above-mentioned laminate and the chlorine atom-containing resin layer are separately provided, or the above-mentioned laminate and the chlorine atom-containing resin layer may be provided. It may be provided in an integrated configuration with a release liner interposed between the and.

As shown in FIG. 1, the indicator having such a configuration can be used by adhering the adhesive layer 103 of the laminate to the chlorine atom-containing resin layer 105.

FIG. 2A shows an indicator 200 having a structure capable of forming a folded portion capable of contacting the chlorine atom-containing resin layer 205 and the adhesive layer 203 containing a dehydrochloric acid agent. Here, the “folded portion” includes, for example, a bent portion in which an adhesive layer is not formed, as shown on the right side of FIG. 2B.

In the indicator 200 shown in FIG. 2, a release liner 202 is applied to protect the adhesive layer 203, and a barrier layer 204 is applied to avoid contact between the chlorine atom-containing resin layer 205 and the adhesive layer 203. ing. An indicator having such a configuration is obtained by peeling off the release liner 202 at the start of use and then folding back the chlorine atom-containing resin layer 205 to which the adhesive layer 203 is not applied so as to be bonded to the surface of the adhesive layer 203. Alternatively, the adhesive layer 203 can be used by folding back so as to be bonded to the chlorine atom-containing resin layer 205 to which the adhesive layer 203 is not applied.

As a modification of the indicator having such a configuration, for example, a film-like base material can be adopted instead of the chlorine atom-containing resin layer 205 of FIG. In this case, for example, in the arrangement configuration shown in FIG. 2A, an adhesive layer and a release liner are applied on the base material, and a chlorine atom-containing resin layer is provided on the right side of the base material at intervals. It may be applied. In the case of such a configuration, the barrier layer can be omitted.

FIG. 3 shows an indicator 300 having a structure in which a pullable release liner 302 is provided between a laminate having a base material 301 and an adhesive layer 303 containing a dehydrochloric acid agent and a chlorine atom-containing resin layer 305. At the start of use, the indicator having such a configuration pulls out the release liner 302 and then presses the outside of the base material 301 or the chlorine atom-containing resin layer 305 to bring the chlorine atom-containing resin layer 305 into contact with the adhesive layer 303. Can be used by

The pulling means of the peeling liner 302 is not particularly limited, and for example, the fixing member 306 of the peeling liner as shown in FIG. 3 can be adopted. The fixing member 306 can be prepared by using, for example, an adhesive containing no dehydrochloric acid, or can be pulled out by a perforation, a crease, a fitting structure, a hook-and-loop fastener, a magnet, or the like. A member having a structure that can be temporarily integrated with the above may be adopted. The fixing member 306 shown in FIG. 3 is intended to use an adhesive, and FIG. 3B shows a state in which the fixing member 306 is crushed by pressing from the base material 301 side. Shown.

FIG. 4 shows an indicator 400 having a structure in which a release liner 402 and a chlorine atom-containing resin layer 405 are alternately laminated on an adhesive layer 403 containing a dehydrochloric acid agent applied on a base material 401. At the start of use, the indicator having such a configuration peels off the chlorine atom-containing resin layer 405 from the release liner 402 and then peels off the release liner 402 from the adhesive layer 403 as shown in FIG. 4B. Then, as shown in FIG. 4 (c), it can be used by bringing the chlorine atom-containing resin layer 405 into contact with the exposed surface of the adhesive layer 403.

In addition, in some embodiments, various modifications can be made to the configuration of the indicators of the present disclosure as needed. For example, in order to suppress the volatilization of the dehydrochloric acid agent from the adhesive layer, or to prevent the influence of moisture, moisture, etc. from the surroundings, an indicator as shown in FIGS. The adhesive layer containing hydrochloric acid and the chlorine atom-containing resin layer may be brought into contact with each other and then encapsulated in the packaging material. Further, a magnet, an adhesive, a hook-and-loop fastener or the like may be applied to at least a part of the outer surface of the indicator as shown in FIGS. 1 to 4 or the outer surface of the packaging material containing the indicator.

When a packaging material is used, the material is not particularly limited, but it is advantageous to use a transparent material at least in the part where the color change is observed. Examples of the packaging material include polyolefins such as polyethylene, polyesters such as polyethylene terephthalate (PET), polyamides, ethylene-vinyl alcohol copolymers (EVOH), polyvinylidene chloride (PVDC) and other chlorine atom-containing resins, and polychloro. Examples thereof include ethylene-based unsaturated polymers such as trifluoroethylene, polyvinylidene (PAN), and cyclic olefin-based polymers. These can be used alone or in combination of two or more.

In order to suppress the volatilization of the dehydrochloric acid agent from the adhesive layer in the packaging material, or to prevent the influence of moisture, moisture, etc. from the surroundings, the packaging material is composed of a material having barrier performance. Is preferable. As such a material, for example, an ethylene-vinyl alcohol copolymer (EVOH) or a cyclic olefin polymer can be used, or, for example, an aluminum vapor-deposited film is formed on at least one side of a film containing the above resin material. , A film prepared by applying an inorganic vapor-deposited film such as a silica vapor-deposited film, a silicon nitride vapor-deposited film, an alumina vapor-deposited film, or a dual vapor-deposited film of silica / alumina can be used.

<Usage of indicator>
The indicator of the present disclosure has the ability to change the degree of coloring of the chlorine atom-containing resin layer according to the temperature and / or time when the chlorine atom-containing resin layer is brought into contact with the adhesive layer containing a dehydrochloric acid agent. .. The indicator of the present disclosure can be changed to a predetermined color, for example, from white to black as shown in FIG. 5, depending on the type or amount of the dehydrochloric acid agent. The time until the color becomes a predetermined color varies depending on the temperature conditions, but even if the temperature of the usage environment is constant or indefinite, for example, by setting the time when the color becomes black as the replacement time, storage period, etc. , The optimum replacement time for products with indicators can be visually determined.

In some embodiments, the indicators of the present disclosure are, for example, articles whose performance is likely to change depending on the temperature of the environment of use, storage period, etc., for example, foods (eg, fresh foods, frozen foods, etc.), beverages, daily necessities (eg, for example). It can be used to check the shelf life, replacement time, etc. of various oils (eg olive oil, lubricating oil, etc.) such as pharmaceuticals, cosmetics, insect repellents, etc.

The temperature of the operating environment of the indicator of the present disclosure is not particularly limited, but may be, for example, −50 ° C. or higher, −40 ° C. or higher, −30 ° C. or higher, −20 ° C. or higher, or −10 ° C. or higher. The upper limit of the temperature of the operating environment is not particularly limited, but may be, for example, 80 ° C. or lower, 70 ° C. or lower, 60 ° C. or lower, 50 ° C. or lower, 40 ° C. or lower, 35 ° C. or lower, or 30 ° C. or lower. ..

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, the blending amount is shown in% by mass.

<< Examples 1 to 7 and Comparative Example 1 >>
The following evaluations were performed on the adhesive composition or the filter paper impregnating solution having the composition shown in Table 1 and the indicator obtained by the production method shown below, and the results are shown in Table 1. In Table 1, the concentration of the dehydrochloric acid agent in the composition or the solution with respect to the total amount of the adhesive composition or the filter paper impregnating solution is "dehydrochloric acid agent concentration (mass%)", and the drying conditions of the adhesive layer in the oven are shown. Notated as "drying conditions".

Further, piperidine and 1,1,3,3-tetramethylguanidine used in Examples and Comparative Examples correspond to amines, and 1,1,3,3-tetramethylguanidine corresponds to the nitrogen atom-containing compound of Formula 1.

<Evaluation method>
(PH test)
The pH of the prepared adhesive composition or filter paper impregnation solution was adjusted to 25 ° C. using a pH meter (desktop pH / water quality analyzer F74, electrode: long ToupH electrode 9680S-10D) manufactured by Horiba Seisakusho Co., Ltd. It was measured by the glass electrode measurement method.

(Color change test: uniformity)
Under the storage temperature shown in Table 1, visually observe the state of color change 5 hours after placing the indicator immediately after manufacturing, and if uniform color change occurs, "A", no color change. The case where it was uniform was evaluated as "B", and the case where no color change occurred was evaluated as "C". Here, in the present disclosure, the A evaluation can be regarded as a pass, and the B to C evaluations can be regarded as a failure.

(Color change test: L value)
The brightness (initial L value) of the indicator immediately after production was measured using a Macbeth color difference meter (Spectro Eye, manufactured by X-Rite). Next, the indicator was placed under the storage temperature shown in Table 1, and the brightness (end point L value) at the time when the color change of the indicator did not occur was measured in the same manner using a Macbeth color difference meter. Further, the values obtained by subtracting the end point L value from the initial L value are summarized in Table 1 as ΔL values.

(Color change speed test)
Immediately after manufacturing, the indicator is placed under the storage temperature shown in Table 1, and the change in the L value of the indicator is measured using a Macbeth color difference meter (Spectro Eye, manufactured by X-Rite) at predetermined time intervals. The time at the time of entering the range of 30 ± 3 was measured.

(Odor test)
The prepared adhesive composition or filter paper impregnation solution was filled in a sample bottle. Under the storage temperature shown in Table 1, the odor from the mouth of the sample bottle was smelled, and the case where no odor was felt was evaluated as "no", and the case where the odor was felt was evaluated as "yes".

<Manufacturing method of indicator>
(Example 1)
The adhesive composition having the composition shown in Table 1 was coated on a 125 μm thick polyethylene terephthalate film (E5100, manufactured by Toyobo Co., Ltd.) using a bar coater, and then dried under the drying conditions shown in Table 1 to obtain a thickness. An adhesive layer of about 20 μm was prepared. A polyvinylidene chloride (PVDC) film (NEW Clerup ™, thickness 10 μm, manufactured by Kureha Corporation) was placed on the obtained adhesive layer to prepare a laminate. A laminate cut into a square of about 5 cm is made into a bag by laminating the periphery of the three sides of a transparent vapor-deposited film (GX film, manufactured by Toppan Printing Co., Ltd.) having barrier performance and a non-stretched polypropylene film via an adhesive layer. The indicator of Example 1 was prepared by arranging it in the packaging material and sealing and packaging it.

(Examples 2 to 7)
Indicators of Examples 2 to 7 were prepared in the same manner as in Example 1 except that the adhesive composition having the composition shown in Table 1 and the drying conditions were adopted.

(Comparative Example 1)
0.5 ml of a filter paper impregnating solution having the composition shown in Table 1 is impregnated in a 2.5 cm square filter paper, and a 2 cm square polyvinylidene chloride (PVDC) film (NEW Kureha ™, thickness 10 μm, stock) is impregnated on the filter paper. A laminate was prepared by arranging (manufactured by Kureha Corporation). Inside a 3.0 cm square packaging material made by laminating the periphery of the three sides of a transparent vapor-deposited film (GX film, manufactured by Toppan Printing Co., Ltd.) with barrier performance and a non-stretched polypropylene film via an adhesive layer. The prepared laminate was placed in, sealed and packaged to prepare the indicator of Comparative Example 1.

<result>
As is clear from Table 1, the indicator of Comparative Example 1 having the dehydrochloric acid agent in the form of a solution had color change but also color unevenness at the same time. On the other hand, in the case of the indicators of Examples 1 to 7 having the dehydrochloric acid agent in the form of an adhesive layer, it was confirmed that color unevenness did not occur and uniform and excellent color change performance could be exhibited.

The adhesive compositions of Examples 1 and 2 had an amine odor, but the adhesive compositions of Examples 3 to 7 did not have an offensive odor such as an amine odor. Therefore, it was confirmed that by using a dehydrochloric acid agent other than amine, an indicator that does not bother the odor can be produced at the time of manufacturing the indicator and at the time of its use.

Further, when the indicators of Examples 1 and 2 were compared, when the drying temperature at the time of forming the adhesive layer was high, the end point L value was high and the color change performance was deteriorated. It is considered that this is because piperidine volatilized from the adhesive layer as the drying temperature increased. On the other hand, in the case of the indicators of Examples 3 and 4, the value of the end point L value was almost the same even when the drying temperature at the time of forming the adhesive layer was high. From this result, in the case of an adhesive layer prepared using an adhesive containing a dehydroxylating agent, a dehydrogenating agent having a boiling point or decomposition temperature higher than that of piperidine (boiling point: 106 ° C.), for example, guanidine (decomposition temperature: 160 ° C.) ℃), The use of nitrogen atom-containing compounds such as 1,1,3,3-tetramethylguanidine (boiling point: 160-162 ° C) has been found to be advantageous.

Further, as is clear from the results of Examples 4 to 6, it was found that the higher the storage temperature of the indicator, the shorter the time required for the color to change to a predetermined color, that is, the faster the color change rate. ..

In the following, when a nitrogen atom-containing compound having a specific structure as represented by the above formulas 2 to 4 and a basicizing agent are used in combination using a reference example and a reference comparative example, a chlorine atom It is shown that the color changing action of the contained resin can be exhibited.

<< Reference Examples 1 to 5 and Reference Comparative Examples 1 to 7 >>
The filter paper impregnating solution having the composition shown in Table 2 and the indicator obtained by the production method shown below were evaluated as follows, and the results are shown in Table 2. In Table 2, the compound to be blended in the filter paper impregnating solution is "compound", the concentration of the compound in the solution with respect to the total amount of the solution is "compound concentration (% by mass)", and the basicization in the solution with respect to the total amount of the solution. The concentration of sodium hydroxide, which is an agent, is referred to as "NaOH concentration (% by mass)", and the diluting solvent blended in the solution is referred to as "solvent".

Further, urea corresponds to the nitrogen atom-containing compound of the above formula 2, dodecylamine hydrochloride corresponds to the nitrogen atom-containing compound of the above formula 3, and lauryltrimethylammonium = chloride used in the preparation of the filter paper impregnating solution. It corresponds to the nitrogen atom-containing compound of the formula 4. Piperidine, which is an amine, does not correspond to the nitrogen atom-containing compound represented by the above formulas 2 to 4.

<Evaluation method>
(Odor test)
The prepared filter paper impregnation solution was filled in a sample bottle. Under the storage temperature shown in Table 2, the odor from the mouth of the sample bottle was smelled, and the case where no odor was felt was evaluated as "no", and the case where the odor was felt was evaluated as "yes".

(PH test)
The pH of the prepared filter paper impregnation solution was adjusted to 25 ° C. by a glass electrode measurement method using a pH meter (desktop pH / water quality analyzer F74, electrode: long ToupH electrode 9680S-10D) manufactured by Horiba Seisakusho Co., Ltd. It was measured.

(Color change test)
^{The hue (a *} ₁ , b ^* ₁ ) and brightness (L ^* ₁ ) of the indicator immediately after production were measured using a Macbeth color difference meter (Spectro Eye, manufactured by X-Rite). Next, the indicator is placed under the storage temperature shown in Table 2, and the hue (a ^* ₂ , b ^* ₂ ) and the brightness (L ^* ₂ ) at the time (end point) when the hue and brightness of the indicator do not change are set. The same measurement was performed using a Macbeth color difference meter.

The obtained measurement results were introduced into the following equation 5 to calculate the ^{color difference (ΔE *} _ab):

It ^{can be said that the larger the ΔE *} _ab value, the better the color change performance. In Table 2, in the item of "color changeability", ^{those having a ΔE *} _ab value of 3.0 or more are “A”, those having a ΔE * ab value of 1.5 or more and less than 3.0 are “B”, and 1. Those that were less than 5 are written as "C". Here, the A evaluation can be regarded as passing, and the B to C evaluations can be regarded as failing.

(Color change speed test)
Immediately after manufacturing, the indicator is placed under the storage temperature shown in Table 2, and the change in the L value of the indicator is measured using a Macbeth color difference meter (Spectro Eye, manufactured by X-Rite) at predetermined time intervals. The time at the time of entering the range of 70 ± 3 was measured.

<Manufacturing method of indicator>
(Reference example 1)
0.5 ml of a filter paper impregnating solution having the composition shown in Table 2 is impregnated in a 2.5 cm square filter paper, and a 2 cm square polyvinylidene chloride (PVDC) film (NEW Kureha ™, thickness 10 μm, stock) is impregnated on the filter paper. A laminate was prepared by arranging (manufactured by Kureha Corporation). Inside a 3.0 cm square packaging material made by laminating the periphery of the three sides of a transparent vapor-deposited film (GX film, manufactured by Toppan Printing Co., Ltd.) with barrier performance and a non-stretched polypropylene film via an adhesive layer. The prepared laminate was placed in, sealed and packaged to prepare the indicator of Reference Example 1.

(Reference Examples 2 to 5 and Reference Comparative Examples 1 to 7)
Indicators of Reference Examples 2 to 7 and Reference Comparative Examples 1 to 3 were prepared in the same manner as in Reference Example 1 except that the filter paper impregnating solution having the composition shown in Table 2 was used. Since sodium hydroxide was difficult to dissolve in the filter paper impregnating solution in Reference Example 4, the concentration was set to 0.4% by mass, unlike other Reference Examples.

<result>
As is clear from Table 2, the single use of a specific nitrogen atom-containing compound such as lauryltrimethylammonium = chloride and the single use of a basicizing agent (sodium hydroxide) having a concentration of about 10% by mass contain chlorine atoms. It was confirmed that while the color change of the resin was not caused, excellent color change performance could be exhibited when a specific nitrogen atom-containing compound and a basicizing agent were used in combination.

Further, in the case of a nitrogen atom-containing compound such as arginine, which does not correspond to the nitrogen atom-containing compound represented by the above formulas 2 to 4, even if such a compound and a basicizing agent are used in combination, the compound may be used in combination. It was found that good color change performance could not be exhibited. From this result, it is not that any nitrogen atom-containing compound can cause a good color change of the chlorine atom-containing resin when used in combination with a basicizing agent, but a specific nitrogen atom-containing compound and a basicizing agent are used in combination. In that case, it was confirmed that good color change could occur.

It has been confirmed that by using the specific nitrogen atom-containing compound of the present disclosure, it is possible to produce an indicator that does not cause an odor during the production and use of the indicator.

It was also found that the higher the storage temperature of the indicator, the shorter the time required for the color to change to a predetermined color, that is, the faster the color change rate.

100, 200, 300, 400 Indicator 101, 301, 401 Base material 202, 302, 402 Release liner 103, 203, 303, 403 Adhesive layer containing dehydrochloric acid agent 204 Barrier layer 105, 205, 305, 405 Chlorine atom-containing resin Layer 306 Fixing member

Claims (12)

An indicator having a chlorine atom-containing resin layer and an adhesive layer containing a dehydrochloric acid agent. The indicator according to claim 1, wherein the chlorine atom-containing resin layer contains at least one selected from a polyvinyl chloride-based resin and a polyvinylidene chloride-based resin. The dehydrochloric acid agent is selected from an amine, a nitrogen atom-containing compound represented by the following formula 1, and a mixture of at least one nitrogen atom-containing compound selected from the following formulas 2 to 4 and a basicizing agent. The indicator according to claim 1 or 2, which is at least one of the following:

In formula 1,
R ^{1 to} R ⁵ are independently hydrogen or alkyl groups having 1 to 10 carbon atoms. However, R ¹ may ^{be linked to R 3} and R ² to R ⁵ to form an alkylene group having 2 to 6 carbon atoms, and when all of ^{R 1 to} R ^{5 are hydrogen.} except for.
In formulas 2 to 4,
R is independently an alkyl group having 1 to 20 carbon atoms or hydrogen.
In formula 3,
A is HF, HCl, HBr or HI,
In formula 4,
X ⁻ is F ⁻ , Cl ⁻ , Br ⁻ or I ⁻ . The indicator according to claim 3, wherein the basicizing agent is an alkali metal hydroxide. The dehydrochloric acid agent contains the nitrogen atom-containing compound, and the nitrogen atom-containing compound is 1,1,3,3-tetramethylguanidine, 1,5,7-triazabicyclo [4.4.0. The indicator according to claim 3 or 4, which is at least one selected from deca-5-ene, urea, dodecylamine hydrochloride, and lauryltrimethylammonium-chloride. The indicator according to any one of claims 1 to 5, further comprising at least one selected from a release liner, a substrate, and a barrier layer. The indicator according to any one of claims 1 to 6, wherein the color change reaction is started by bringing the chlorine atom-containing resin layer into contact with the adhesive layer. The indicator according to any one of claims 1 to 7, wherein a folded portion capable of forming a folded portion capable of bringing the chlorine atom-containing resin layer into contact with the adhesive layer can be formed. The indicator according to any one of claims 1 to 7, further comprising a pullable release liner between the chlorine atom-containing resin layer and the adhesive layer. It has a structure in which a release liner and a chlorine atom-containing resin layer are alternately laminated on the adhesive layer, and after the chlorine atom-containing resin layer is peeled off from the release liner, the release liner is peeled off from the adhesive layer. The indicator according to any one of claims 1 to 7, wherein the chlorine atom-containing resin layer can be brought into contact with the adhesive layer thereafter. The indicator according to any one of claims 1 to 10, which is used in an environment of −50 ° C. or higher. The adhesive composition for an indicator according to any one of claims 1 to 11, which comprises a dehydrochloric acid agent.

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